Iron and Manganese

Iron and manganese control is the most common type of municipal water treatment in
Minnesota. Iron and manganese occur naturally in groundwater. Neither element causes adverse
heath effects at concentrations typically found in Minnesota. These elements are, in fact,
essential to the human diet.
Water containing excessive amounts of iron and manganese can stain clothes, discolor plumbing
fixtures, and sometimes add a rusty taste and look to the water. Surface water generally does
not contain large amounts of iron or manganese, but iron and manganese are found frequently in
water systems that use groundwater.
The Safe Drinking Water Act secondary standards (aesthetic, not health related) for iron in
drinking water is 0.3 parts per million (ppm) and 0.05 ppm for manganese. If water contains
more than 0.05 ppm iron, or 0.01 ppm manganese, the operator should implement an effective
hydrant-flushing program in order to avoid customer complaints.
BACTERIA AND IRON AND MANGANESE
Iron and manganese in water also promote the growth of bacteria (including iron bacteria). These
organisms obtain energy for growth from the chemical reaction that occurs when iron and
manganese mix with dissolved oxygen. These bacteria form thick slime growths on the walls of
the piping system and on well screens. These shines tend to be are rust-colored from iron and
black-colored from manganese. Variations in flow can cause these slime growths to separate
from pipe walls, resulting in dirty water in the system.
The growth of iron bacteria can be controlled by chlorination. However, when water containing
iron is chlorinated, the iron is converted from the ferrous state to the ferric state--in other words,
rust--and manganese is converted into black manganese dioxide. These materials form a coating
on the inside of the water main and, when they break loose, a customer will sometimes complain
of dirty water.
Iron bacteria will use even small amounts of iron present in the ferrous state, oxidize it, and then
use the energy. Manganese is also used by other bacteria to form organics, which contribute to
the iron bacteria slime in the well and/or water system.
Iron bacteria are found any where a food source of iron is available. The presence of one
bacterium is all that is needed to start an infestation in a well or a distribution system.
IRON AND MANGANESE CONTROL
Methods to control iron and manganese in distribution systems include arranging for alternate
water sources, adding phosphate to the water to keep iron and manganese in solution, and
oxidizing and removing both by filtration.

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Alternate Sources
In some situations, abandoning a well and drilling a new one into an aquifer with a lower iron or
manganese concentration may be cost-effective. It may also be possible to blend the water from
the well with the high concentrations with water from another source with lower concentrations.
Phosphate Treatment
Phosphate can be added at the source to mask the effects of elevated iron concentrations in the
distribution system. This is effective when the water contains less than 0.3 ppm of iron or 0.1
ppm of manganese. Phosphate delays the precipitation of oxidized manganese and iron, thereby
greatly reducing the layer of scale that forms on the pipe. The effect is called sequestration. The
iron or manganese ion is surrounded by a chain of phosphate molecules and is not allowed to
precipitate in the water.
Pyrophosphate, tripolyphosphate, and metaphosphate may be effective as iron and manganese
sequestering agents. However, the most effective seems to be sodium phosphate in low
concentrations. The proper dose and type of phosphate should be selected only after bench-scale
testing is performed by a qualified technician or consultant.
Phosphate feed points should be separated from the chlorine injection point by as much distance
as possible. The phosphate feed point should also be ahead of the chlorine injection point. If
phosphate is fed after chlorine, there is a possibility the iron and manganese will be oxidized by
the chlorine before sequestering can take place causing iron and manganese precipitates to be
pumped out into the distribution system.
Feed equipment used for phosphate
addition is similar to equipment used to
feed fluoride. It consists of a storage
tank, solution tank, feed pump, and
controller to pace the feed rate. The
storage tank and solution tank must
contain at least 10 ppm of free chlorine
residual to prevent bacterial growth in
the phosphate solution (phosphate is an
excellent food source for bacteria).
Phosphate solutions can be made up
from powder in a saturator similar to the
one used to make dry-fluoride solutions
(see Fluoridation). Phosphate solutions
containing more than one-half pound of phosphate per gallon (60 ppm) may be very viscous. It is
important that any solution be fed within 48 hours of its production. Polyphosphates tend to
break down into orthophosphate, which is much less effective in preventing manganese deposits.

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The amount of phosphates required to sequester iron and manganese generally has to be
approximately two parts actual phosphate (as product) for one part of iron and manganese. It is
also important to remember that a chlorine residual must be maintained throughout the
distribution system to control bacterial growth. The chlorine residual should be greater than 0.2
ppm at the most distant part of the system.
If the total detention time in the distribution system exceeds 72 hours, the phosphates may break
down and release the iron and manganese in the outer portions of the system. If the detention is
exceeded, the iron or manganese problem may not be resolved with phosphate.
Removal by Ion Exchange
Ion exchange may also remove iron and manganese (typically used in home softening). If the
water has not been exposed to oxygen, the resins in the softener will remove the iron and
manganese ions from the water. If the water contains any dissolved oxygen, the resin can be
fouled with iron and manganese deposits. The resin can be cleaned, but the process is expensive
and the capacity of this resin is reduced with each cleaning. This method is not recommended for
municipal treatment.
Removal by Iron and Manganese Filtration
Removing iron and manganese from drinking water instead of sequestration it is recommended if
the water contains over 0.3 ppm of iron or 0.05 ppm of manganese. These elements can be
removed during softening with lime, but most commonly iron and manganese is removed by
filtration after oxidation (with air, potassium permanganate, or chlorine).
Gravity and pressure filters are both used, with pressure filters being the more popular.
The operator should frequently check to see that all the iron in the water entering the filter has
been converted to the ferric (or insoluble particulate) state. The operator collects a water sample,
passes it through a filter paper, and runs an iron test on the clean, filtered water (filtrate). If no
iron is present, it has all been oxidized and is being removed in the filtration process. If iron is
found in the filtrate, oxidation has not been complete and some of the iron will pass through the
filter and end up in the treated water. In this case, the operator should consider adjustments to the
oxidation process.
Most iron removal filters are designed so that the filters are backwashed based on head-loss on
the filter. If iron breakthrough is a problem, the filters will have to be backwashed more
frequently. Accurate records will reveal when breakthrough is expected so that the operator can
backwash before it is likely to occur.
Oxidation with aeration
Iron is easily oxidized by atmospheric oxygen. Aeration provides the dissolved oxygen needed to
convert the iron and manganese from ferrous and manganous (soluble) forms to insoluble

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oxidized ferric and manganic forms. It takes 0.14 ppm of dissolved oxygen to oxidize 1 ppm of
iron, and 0.27 ppm of dissolved oxygen to oxidize 1 ppm of manganese.
Aeration requires careful control of the water flow through the process (see Aeration chapter). If
water flow is too great, not enough air is applied to oxidize the iron and manganese. If water
flow is too small, the water can become saturated with dissolved oxygen and, consequently,
become corrosive to the distribution system. Corrosive water may lead to increased lead and
copper levels at customers taps.
During aeration, slime growths may develop on the aeration equipment, and if these growths are
not controlled, they can produce taste and odor problems in the water. The growth of slime can
be controlled by adding chlorine at the head of the treatment plant. The process should be
inspected regularly to catch problems early.
A detention basin can be provided after aeration to allow complete oxidation. These basins
should be cleaned regularly to avoid sludge accumulation. Detention time can also be provided
with head on the filters rather than requiring a separate tank. Detention time before filtration
should be at least 20 minutes, more if possible. The pH of the water influences how much time is
needed for the reaction to be completed. After oxidation of the iron and manganese, the water
must be filtered to remove the precipitated iron and manganese.
Oxidation of iron and manganese with air is by far the most cost-effective method since there is
no chemical cost; however, there are disadvantages. The oxidation process can be slowed and the
reaction tank has to be quite large (if there are high levels of manganese). In addition, small
changes in water quality may affect the pH of the water and the oxidation rate may slow to a
point where the plant capacity for iron and manganese removal is reduced.
Oxidation with chlorine
Iron and manganese in water can also be oxidized by chlorine, converting to ferric hydroxide and
manganese dioxide. The precipitated material can then be removed by filtration. The higher the
amount of chlorine fed, the more rapid the reaction. Most treatment plants use 1 2 parts of
chlorine to 1 part of iron to achieve oxidation.
When using this process on water containing organics such as Total organic carbon (TOC) or
natural organic material (NOM), the likelihood of creating disinfection by-products (DBPs)
increases.
Oxidation with permanganate
Using potassium permanganate to oxidize iron or manganese is fairly common in Minnesota.
Potassium permanganate oxidizes iron and manganese into their insoluble states. The dose must
be great enough to oxidize all of the manganese, but not too great as this will produce a pink
color in the water in the distribution system. Observing water being treated will indicate if
adjustments to the chemical feeders are needed. Potassium permanganate is typically more
effective at oxidizing manganese than aeration or chlorination.

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When oxidizing with potassium permanganate, the operation of the filters becomes important
since the reaction also continues to take place in the filter media. The normally-used filter media
(sand) will remove iron and manganese if the combined concentration is below 1 ppm. Higher
concentrations require different type of filter materials (greens and others) and different methods
of operation.
Potassium permanganate is often used with manganese greensand, a granular material that is
charged with potassium permanganate after the backwashing process. This method allows the
oxidation process to be completed in the filter itself and is a buffer to help avoid pink water in
distribution. After the filter is backwashed, it regenerates for a period of time with a high level of
permanganate before it is put back into operation.

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Notes:

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